Preparation of silicon-containing heteropolymers



Patented Mar. 24, 1953 UNITED: Sr; OFFICE PREPARATIONQF:$ILICON-CONTAINING3 HETEROPOLYMERS Raymond 1 Biumjell; Toledm'aiOhio, @assi'gnor to Libbeyt-OWenS Ford Glass; Companm', Tolcdoi Ohio; a corpor'atioxr of Ohio NW Drawing. Applicatioiivofctolfer fi 191F751 ScriaLNo. 777%02- 28 01511518. (G1, EGG-46.5%

' Thennvention relatesito thepreparation' off- 7 silicon 'containing heteropolymers and particularly'to a novel heteropolymerization reaction and novel products resultingtherefrom.

Copolymerization i's the simultaneous polymerization of. two. on moresubstances .to: formmoler culs madlnp oflunitslderived from both.- substances. Hteropolymeriz'ationi is avspecialmcasel of .lcopolymerizationa namely; the copolymerizationlof two. unsaturated substances. at least one ofi whichadoesunot readil'ypolymerize alone.

IhlUiiitedlStates Patent No.- 2 388,16 1- it is ireportedi that tetraeallylsilane .is la polymerizable: substanoe,L-.- that it" can: .bespolymeri'zeda alone i by; the use of conventionalpolymerization procedures and that it can be copolymerized with a: large variety of other. polymerizable .substances; Tetra-allylsilane, however, has the disadvantages that it is very expensive to produce and that its copolymerizationwitl'i' other polymerizable materials, becauseeof the presence of so many allyl radicals in its molecule, causes excessive'cross-" linking which leads to severe shrinkagebrit tleness and other difiiculties.

The principal object of'the invention is the preparation of new and improved silicon comtaining heteropolymers and useful derivatives thereof. More specific objects and advantages are apparent from: the description, which merely illustrates and discloses the invention and is notintendeclto impose limitations upon the claims.

It has been founilithat a silane whose molecule consists of a silicon atom connected to four monovalent radicals, at least one of whichlis. an alkoxy radical," and at least one of which is a methal1y1 radical; is" not" a" polymerizable" subthe discoverythat such an ester. 'orianhyurid;

polymerizes-readily*witlifasilanec'wliose"molecule: consistsnf a silicon atom attachedto 'fourmonm va-ln't ra'dicals;"at least "one -of..vvh'ichisan alk'oxyf radical, and the" remainderofwhiclti. are hydrocarbon radicals including atfl'ast "one 'methall'yl radicalf The polymerization'i of these two com: ponents -is=a=true heteropolymerization"because each "oftlie two componentsis t'sub'stantiallyfun polymeriaabl aloner l 2:; Theipresentinvention.isextremely versatile in: that tli'ezmol eoul efof thei'silan'ez'mayi contain vari ousi'alkoxyei radicals and various saturatedliy:-- drlocarbon radicalsandzincthat the moleculerof the iesterrmayrcontain various alcohol radicals;

soi that it'iis' 'possible: to produce: heteropolymers' having .widelyivariedaiproperties fittingethem for" manyirdifferent uses} If the SiIaI'lB COIIEaiHSi more than'nonesmethallyll radicaL-aorfif the ester conble bond, the polymerization is accompaniediibyi OIOS'S-linkil'lgiSOfIthEtiit-DFOdHCBS anxiniusible; insolublez resin'i; Thea.este1=,:if.:it contains mo'rerthan one rolefinicsdouble bond; \mayr'be. polymerizable alonem Polymerization lofiisuchsanz ester with a silaneviniaccordariceawith' .the invention produces: a'inew result ,however;-;-inl thatlltheisilane vactuallyi oopolymerizes with lthe' ester so as'to introduce: silicon-intoarthe resinirnolecule;- thereby imparting. valuables new properties to'itheiresin; i

It 111113118 practic'etof the: invention laavsil ane l corrtainirig-Zonlytone methallyl radicalfispolymerized': with an estericontainingonly one :olefinic idoublefl bond-, the resulting heteropolymeriordinarilytis fusible: and mays-b'e' ailiquid Such arheteropo'lya merf has valuablerproperties%that-- are due' to the: presence-iofialkoxyf radicals :in: the :heteropolymer moleculessvv 'I -he presence of :these :alkoxy :radicals pemnits theicarryingi out of aifurthei raction inwhich: .theialkoxyrradicalsrare -hydrolyzed to' hy droxy radicals -which=then are condensed with" one another. The condensationt oftwo hydroxyr radicalsson itwo difierent v molecules produces :an oxygen linkage and -thereby; cross-links :the qnolecul es toy produce: an infusible,-:-insoluble resin. Thus the fusible heteropolymer-s =-of the present s invention; are-l-val uable= intermediates -which by hydrolysis i and: condensation can-be converted into infusiblearesinst The-'practicelof the iinvention requires' theprep arationl pill a; polymerizablel composition" whichcomprises (a) 'maIeic an-hydride, or a symmetricalor mix'ed'ester of maleic or fumaric acid -iin- Whicheach of the.alcohol radicals isallyl; mathauyr; l chloro -2 propyl, 2-cliloroethylj benzyll tetrahydrofurfuryl, lcyclohexyLl phenyl,,;o-cresyl, m=cresy1;; rf-crejsyl; methyl}... ethyl, prop ylfl isoprdp n'-butyl; isoloutyljsecondary butylg" .or a primaryInr' secondary. alkyllradical h'avingt-ifrom fiive to eight carbon atoms and;.(b-) a. sillane-havin'g atleastfone'niethallylradicaland at least one: all ijoxyja dical attached to the siliconatom Suchalkoxy'radi'ai"n ayt. bemethoxy; eth oxy ipropoxy isopropo'xygn-"b o' butoxyz other 0 radicalain theasilanemomenta-maybe"tfiesame"radical; or they may iis'ob utoxyi or secondary be two difierent radicals. The silane has one of the following general formulas R is an alkoxy radical hereinbefore described. A and A may be the same or different and each is allyl, methallyl, benzyl, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, secondary butyl, a

-hexyl alcohol, hexan-Z-ol, n-hexyl carbinol, 4-

primary or secondary alkyl radical having from V five to eight carbon atoms, an alkoxy radical hereinbefore described, or a monovalent hydrocarbon radical of the benzene series having the free valence attached to the nucleus, having from six to twenty-one carbon atoms, and having not more than three side chains consisting of alkyl radicals of not more than five carbon atoms (i. e., a phenyl radical, or a mono-, di-, or tri-alkylsubstituted phenyl radical in which the alkyl radicals, if more than one, are the same or dif-, ferent, and each alkyl radical is methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, secondary butyl or tertiary butyl, or a primary, secondary or tertiary alkyl radical having five carbon atoms).

b is a monovalent cycloaliphatic hydrocarbon radical having a single nucleus containing from five to six carbon atoms one of which is connected to the free valence and to a hydrogen atom, an-v other of which, adjacent the first, is connected to two hydrogen atoms, and the rest of which are each connected to at least one hydrogen atom, having from five to sixteen carbon atoms, and having not more than two side chains consisting of alkyl radicals of not more than five heptanol, n-octanol, cyclohexanol, '1-chlcro-2- propanol, Z-chloroethanol, allyl alcohol, methallyl alcohol, benzyl alcohol, tetrahydrofurfuryl alcohol, phenol, o-cresol, m-cresol and p-cresol.

The preferred polymerizable compositions comprise an ester of maleic or fumaric acid in which each of the alcohol radicals is methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, secondary butyl, or a primary or secondary alkyl radical having from five to eight carbon atoms, and a carbon atoms (1. e., a cyclopentyl or cyclohexyl radical, or a monoor di-alkyl-substituted cyclopentyl or cyclohexyl radical in which the alkyl radicals, if more than one, are the same or different, and are attached to difierent nuclear carbon atoms not more than one of which is adjacent the carbon atom attached to the free valence, and each alkyl radical is methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tertiary butyl, or a primary, secondary or tertiary alkyl radical having five carbon atoms).

B is an alkoxy radical hereinbefore described or a radical of the same class as b.

v r is a monovalent hydrocarbon radical of the naphthalene series having the free valence attached to a nucleus, having from ten to twentyfive carbon atoms, and having not more than three side chains consisting of alkyl radicals of not more than five carbon atoms (1. e., a naphthyl radical that is unsubstituted, or is substituted with one, two or three similar or dissimilar alkyl radicals).

sis allyl, methallyl, or an alkoxy radical hereinbefore described. 7

Examples of esters with which the silanes may be polymerized include dimethyl maleate, diethyl maleate, diisopropyl maleate, di-n-propyl maleate, di-act-amyl maleate, diethyl fumarate, dipropyl fumarate, diisopropyl fumarate, diisobutyl fumarate, bis(beta-chloroethyl) fumarate, diact-amyl fumarate, diphenyl fumarate, diphenyl maleate, dibenzyl fumarate, dibenzyl maleate, dip-tolyl fumarate, diallyl maleate, diallyl fumarate, tetrahydrofurfuryl maleate and dimethale silane having one of the above general formulas in which A, B and s are alkoxy radicals hereinbefore described, or a silane having the general formula in which n is an integer from 1 to 3, and R is an alkoxy radical hereinbefore described. The preferred alkoxy radical is ethoxy.

Methallylalkoxysilanes are prepared by the procedure described in Example 1. Alkoxysilanes having one or two methallyl radicals attached to the silicon atom are reacted with a Grignard reagent to prepare further-substituted silanes, according to Equation 1, 2 or 3 (below).

CH3 CH: G R

II R! in which X is a chloro, bromo, or iodo radical; each of the radicals R, R and R" is an alkoxy radical hereinbefore described; R, R and B may be the same or different; each of the radicals u and u is of the class consisting of benzyl, alkyl radicals having from one to eight carbon atoms and having at least one hydrogen atom attached to the same carbon atom as the free valence, monovalent hydrocarbon radicals of the benzene series having the free valence attached to the nucleus, having from six to twenty-one carbon atoms, and having not more than three side chains consisting of alkyl radicals of not more than five carbon atoms, and monovalent cycloaliphatic hydrocarbon radicals having a single nucleus containing from five to six carbon atoms one of which is connected to the free valence and to a hydrogen atom, another of which,

by using less than about mol of a hydrocarbon magnesium halide per mol of a methallylalkoxysilane. It is not economically practicable to prepare a dialkoxysilane by using more than about 1% mols of a hydrocarbon magnesium halide per mol of a methallyltrialkoxysilane. If it is desired to prepare a monoalkoxysilane, it is preferable to use at least about 1 mols Of a hydrocarbon magnesium halide per mol of a-methallylalkoxysilane, but it is not economically practicable to use more than about 3 mols of a hydrocarbon magnesium halide per mol of a methallylalkoxysilane. The minimum ratio of reactants is that below which a substantial yield of the desired product is not obtained, while the maximum ratio of reactants is that above which the yield of desired silanes (based on the amount of hydrocarbon magnesium halide used) decreases materially, for example, because of byproduct formation. In the preparation of a dialkoxysilane it is most economical to use the hydrocarbon magnesium halide and the. methallyltrialkoxysilane in a molal ratio of about 1:1. In the preparation of a monoalkoxysilane it is most economical to use the hydrocarbon magnesium halide and the methallylalkoxysilane in a molal ratio of about 2:1 or 3:1. For example, when phenyl magnesium bromide (about 18 parts). is reacted with methallyltriethoxysilane (about 22 parts), in a molal ratio of about 1:1, the resulting product contains phenylmethallyldiethoxysilane (about 10 parts). magnesium bromide (about 27 parts) is reacted with methallyltriethoxysilane (about 22 parts),

in a molal ratio of about 1 21, the resulting I product contains phenylmethallyldiethoxysilane (about 7 .parts) and diphenylmethallylethoxw silane (about 4 parts). In the most desirable procedure, the magnesium is added to the flask, and dropwise addition of the halo-substituted hydrocarbon is begun as soon as the Grignard reaction has beeninitiated by means of the starter, hereinbefore described. When the Grignardreaction is proceeding 30 as to be noticeably exothermic the methallylalkoxysilane and ether are added slowly through the reflux condenser. After addition of the methallylalkoxysilane and ether, dropwiseaddition of the halo-substituted hydrocarbon is continued at a rate sumcient to maintain moderate refluxing of the ether;

The reaction takes place readily at ordinary temperatures with noticeable formation of a grayish precipitate and with evolution of heat as soon as the reactants are brought together. Since the reaction is exothermic in nature and becomesextremely violent if the halo-substituted hydrocarbon is" added 'too' rapidly, it 'is usually. desirable to keep the temperature of the" fe'ac tion mixture down to about 40 C. (e. g., by means of an ice bath) so that the halo-substituted hydrocarbon'may be added at a reasonable rate. The reaction may be carried out at com: paratively high temperatures under pressure (e. g., in a bomb), but the maximum temperature at atmospheric-pressure is-the boiling point of the reaction mixture.

The reaction is carried out in the absence of; moisture and oxygen since any water which is present causes hydrolysis of the reactants and the products, and-. any oxygen which is present may decompose the Grignard reagent by oxidation. On the other hand, it is usually desirable to carry out the reaction in the presence of a When phenyl volatile solvent or' diluent, such as (anhydrous) ether.

In the preferred procedure, employing ether, the reactionis carried out in a closed vessel equipped'with cooling means, an agitator and a condenser. Such a reaction is carried out at the reflux temperature of the ether so that the maximum output of heat generated during the reaction may be removed (by way of the reflux condenser). The ether vapor over the reaction mixture serves as a vapor seal to exclude air (containing both moisture and oxygen) .from the reaction. However, the presence of a great'ex: cess of ether may have a tendency to reduce the yield, and the amount of ether used is preferably that amount required to keep the reaction mix ture in a highly fluid state (thereby avoiding points of concentrated reaction), for example, an amount of ether equal to about one-half the weight of the reaction mixture. After the halo-substituted hydrocarbon is addedthe reaction mixture is refluxed for several hours in order to ensure complete reaction. To prepare certain silanes (e. g., alkyland cycloaliphatic-substituted silanes) it is necessary to distill the ether and heat the residue strongly for several hours. pleted, the magnesium salts (in the form of a grayish precipitate) in the reaction mixture are removed. (preferably by filtration), the filter cake is washed with ether or benzene, and'the volatile substances in the reaction mixture, which include byproducts and diluents, are removed by distillation at atmospheric pressure. The. silanes in the product are obtained readily in a subby (vacuum) fractional dispolymerize with almost explosive violence as soon as the polymerization mixture is warmed, as on a steam, bath, and yield a hard, in fusible, and

in somev instances, glass-like heteropolymer. A

possible cause of the formation of an infusible heteropolymer is a reaction between the anhydride linkage and the alkoxy radicals, to give a cross-linked molecule.

. The polymerization of the ester or maleic anhydride with a 'silane having two or three methallyl radicals yields an infusible heteropolymer; likewise, the polymerization of a silane having only one methallyl radical with an ester having two or more polymerizable olefinic double bonds yields an infusible heteropolymer. .There are suiiicient double bonds in these starting materials so that cross linking through double bonds could cause the formation of infusible heteropolymers. In many instances, however; these polymeriza: tions, are stopped before an insoluble, infusible heteropolymer is formed, and a viscous liquidis' o e a The addition polymerization is thought to take place by reaction between the double bonds and toresult in a long-chain, virtually saturated molecule- Figure (a) shows amolecule of dimethyl maleate and a molecule of ;a silane and fleu eai zl. shows;- thei-addition heterop lymcr After the reaction is com.

, acceptswhich we result: from the polymerization of the molecules shown in figure a).

inthe repeating unit indicated in figure (b).

The polymerization takes place when the silane and the anhydride or est-er are brought together, in any ratio, with a catalyst, and is expedited by heating. The catalyst may be "any organic perso oxide, such as benzoyl peroxide, succinyl peroxide; acetyl peroxide, perac-etic acid, perbenzoic acid; toluene peroxide, parabrcmobenzoyl peroxi de; anisoyl peroxide; chloro-a-cetyl peroxide, acetyl benzoyl peroxide, diace-tyl peroxide, or furoyl peroxide, or-any organic ozonid'e, such as d-iiso propyl ozonide, ordiisobutylene ozonide'or a mixture of" such substances. The amount of catalyst used is ordinarily within the range from about 0.05 per cent of the reaction mixture (an amount at which polymerization proceeds at a rate that" at least-appreciable, but not necessarily rapid-enough for practical use) to about 5 per cent (an amount above which no appreciable increase in effect observed). In most cases; ithe'amount of catalyst that causes the reaction toproceed at :the desired rate is from about 011 per cent to about 3 per cent.

In some instances it is desirable to carry out the; polymerization the presence of a solvent}, such as methyl ethyl lt'etone or diorcane, because of the use of immiscible reactants (e. g, maleic. anhydrideand methallyltrieth-oxysilane') The-specific properties of any one heteropclymer can be varied widelyby changingthe ratio. of reactants; so that the proportions of reactants u'seddepend upon the end use" Oli'llh heteropolymer'. However, since the predominant reaction apparently is anqaddition polymerization, and neither component is polymerizable. alone, it is advisable to react the" silane with maleic anhydride" or" the ester in such proportions that tliei-e'is about one methallylradical, containing one o'lefinicd-ouble' bond', per olefinic' double bond in the ma-l'eic anhydride; or in the acid part of the-ester molecule. Olefinic' double bonds in the alcohol part of" the ester molecule are not included in computing this ratio of reactants, although their presence has a material effect on the resulting product (e. g.,'dially1 maleate produces a very hard, tough, clear heteropolymer Withdimethallyldiethoxysilane, whereas, under the same conditions; dime-thyl male-ate produces a weak; soft gel, or a rubbery gel) 'I he rate at which the polymerization proceeds depends upon the reactants" used and the temperature; some reactants: polymerize more readily'thanothers, and the'-po1ymeri zaticnsof maleic anhydride with the silanes are strongly exothermic, self-sustaining reactions, beginning almost as soon as the reactants are: warmed. The temperatureat which the polymerization is conducted is that which gives the desired degree of polymerization in a reasonable time (usually ab-out 24 hours), and usually between 50 and C. for the polymerization of the esters with the silanes.

Although the difli-culty of controlling the polymerization of. a. mixture. of maleic anhydride with one of the silanes is an obstacle in many applications of the polymerized: product, the speed of the polymerization of such a mixture sug ests its use as'a molding; compound The" characteristics of the polymerization re action and of theresulting product depend upon the. silane used (:i. e;, upon what two radicals-,in addition. to the alkoxy and methallyl radicals, are attached to the silicon atom in: the silane: molecule), the ester-or :acidianhydride used, the temperaturev at which. polymerization proceeds,v the time during which polymerization proceeds, and. in. some. instances, the?- amount. of catalyst; For example, maleic anhydride: and methallyl triethoxysilane in a mol-al ratio of 1:11. with 1 per. cent benzoyl' peroxide polymerize in about ten minutes, to yield a thick syrup; maleioi anhy drid'e and dimethallyldiethoxysilane in. a metal ratio of 2:1: with; 1 per cent benzoylp'eroxide, in". an equal volume of dioxane, polymerize iniabout' fifteenrninutes, to yield :a; hard, colorless hetero-- polymer; maleic anhydride and n-butyl methallyldiethoxysilane in: a 11:1 molal ratio:with 1 per cent. benzoyl peroxide, and sufii cient methyl ethyl ketone to give: a one phase solution; polymerizein about thirty seconds, to yield a rubber" like heteropolyme r, which sets to a hard, colorless solid after stanl'iing for several days. The polymerization of the-saturated esters of maleic acid with the methal'lylethoxysilan'es is slower than the polymerization of the corresponding: fumaric acid esters with these: silanes, and the products appear to have a lower molecular weight; and a greater tendency to remain fusible materials; The polymerization of mal'eic anhydride and methallyltriethoxysilane in: a: molal ratio of 1:1v with 5" per: cent benzoyl peroxide proceeds with almost. explosive. violence, as soon: as the reaction mixtureiswarm, to yield a hard, glass-like 'heteropo'lymer' in from one to two" minutes, while the polymerization of malei'c' an-- hydride:- with: methallyltriethoxysi'lane in 213 111 molal ratio" with 1 per cent benzoyl' peroxide, in anequal volume. of dioxane, proceeds in about ten minutes to yield a thick syrup.

The viscosity of a given heteropolymer depends upon the temperature at which the polymerization proceeds, and upon the duration of the polymerization (ex g'., the viscosity ofahetero'polymer of" methallyltriethoxysilane and diethyl fumarate', as determined by efilux time from a 25ml. pipette, varies with polymerization timeat 75 C. as follows: after 18' hours the'effiux' time is 143.0 seconds; after 2?; hoursthe efflux time is 211.2 seconds and after 45" hours the efiiux time is 259 .7 seconds) As at least one alkoxy radical is attached to each silicon atom in the polymer molecules, the polymerized compositions are hydrolyzable, at least in theory. Polymerized compositionshaving' an extremely" high molecular weight are insoluble in ordinary solvents, so that hydrolysis by the usual methods is impossible. However, when the polymerization product is of sufficiently low molecular weight so that it is a liquid or a soluble, fusible solid, hydrolysis after polymerization is possible.

I The reactions of each alkoxy radical which theoretically occur during the course of hydrolysis and condensation are believed to correspond essentially to Equations 4 and (below) 2s|i-oH 11,0 A l-04tin which R is an alkoxy radical.

The hydrolysis of a simple hydrolyzable silane (i. e., of a silane having only relatively simple radicals attached to the silicon atom, and having at least one hydrolyzable radical, such as a halo radical or a primary or secondary alkoxy radical) is likely to be a relatively vigorous exothermic reaction in the presence of an acid catalyst. The intermediate compound, which is known as a silanol (i. e., the product of a reaction corresponding to Equation 4), is known to exist and, in some instances, may be isolated (e. g., diethylsilanediol or diphenylsilanediol); however, sucha compound usually condenses readily to a siloxane (i. e., the product of a reaction corresponding to Equation 5). In the usual hydrolysis reaction of such a simple silane the silanol which is produced is understood to exist in a transitory stage, and concurrently with or immediately after the production of the silanol, it is condensed to form the corresponding siloxane.

The general properties of a completely condensed siloxane (i. e., a siloxane substantially free of hydroxy radicals) prepared from a simple silane depend to a great extent upon the number and type of organic radicals attached to the silicon atoms. Logically, different hydrocarbon substituents impart highly different properties to the siloxane. On the other hand, the number of hydrolyzable groups in the silane that is hydrolyzed determines the number of cross linkages, believed to be SiO.-Si linkages, in the siloxane. It has been found, in general, that silanes containing three hydrolyzable groups in the molecule produce highly cross-linked, three dimensional, solid siloxanes; silanes containing two hydrolyzable groups produce cyclic and linear siloxanes; and silanes containing only one hydrolyzable group form disiloxanes containing only one Si-O--Si linkage in the molecule.

However, silanes which have been subjected to addition polymerization and, therefore, have large complicated radicals attached to the silicon atom, in addition to at least one hydrolyzable radical, condense to siloxanes relatively slowly, and, in many instances, a liquid hydrolysis product is isloated after hydrolysis.

The condensation products or siloxanes embodying the invention contain the characteristic linkage of different silicon atoms to an oxygen atom. Apparently the liquid hydrolysis products contain very few SiO-Si linkages; because of the comparatively high molecular weight of the heteropolymers, relatively little cross-linking (through SiO-Si bonds) would result in insoluble, infusible solids. The liquid products of the hydrolysis of the heteroploymers are condensed to hard infusible solids only under the ac tion of heat.

The polymerized silanes are hydrolyzed by add- 12 ing the silane to a 'hydrolyzing solution of an acid at room temperature, with agitation, and allowing the reaction to proceed for a short time. The hydrolysis product is recovered by extraction with a solvent such as ether and is washed with a reducing solution such as ferrous sulfate, and

. the solution of the extract is dried over sodium sulfate. An inhibitor, if used, is added to the dried solution of the extract. A solvent such as a simple ketone or ester, or one of the lower homologues of benzene, is added to the dried solution of the extract, and the extracting solvent is removed, as by heating on a steam bath.

Usually it is desirable to avoid gelling of the solution of the hydrolyzed heteropolymer. Unless precautions are taken, gelling is likely to occur during removal of the extracting solvent. Apparently, the presence of peroxides increases the tendency of the hydrolyzed heteroploymer to gel. It is, therefore, advantageous to destroy the peroxides, as by washing with a solution of a reducing agent, such as ferrous sulfate. An inhibitor such as hydroquinone or p-aminophenol may be added to the hydrolyzed silane, and will greatly decrease the tendency to gel. However, most inhibitors have a deleterious effect on the hydrolyzed heteropolymers, and it is preferable to avoid their use. a It has been found that the addition of certs solvents to the extraction solution makes it possible to remove the extracting solvent such as ether without gelling the hydrolyzed heteropoly mer. Several of the lower homologues of benzene, such as benzene, toluene and the xylenes, give satisfactory results, but the simple ketones and esters are far more advantageous. Solutions of the hydrolyzed heteropolymers in hydrocarbon solvents have a tendency to gel upon standing; whereas, solutions in ketones are far more stable, and do not gel even after standing for several months. It is believed that the polar molecule of the hydrolyzed heteropolymer is considerably more soluble in the polar ketones and the polar esters than in the non-polar hydrocarbon solvents, and that there is probably some increase in the average molecular weight of the hydrolyzed heteropolymer upon standing, with a corresponding decrease in solubility. This increase in molecular weight is thought to be sufficient to make the hydrolyzed heteropolymer insoluble in the hydrocarbon solvents, so that a gel results. However, in the polar ketone or ester solvents, the hydrolyzed heteropolymer remains soluble even after the increase in molecular weight which accompanies several months standing.

The viscosity of the polymerized silane before hydrolysis seems also to affect the tendency of the hydrolyzed heteropolymer to gel during and after evaporation of the extracting solvent; that is, hydrolysis, of a viscous heteropolymer is more likely to yield a gel during or after evaporation of the extracting solvent than hydrolysis of a less viscous heteropolymer. The viscosity of the polymerized silane is controlled by regulating the temperature and the duration of the polymerization reaction, as hereinbefore described. However, the products of the hydrolysis of even the most viscous heteropolymers of the invention are recovered without gelling by washing the extraction solution with ferrous sulfate, and by adding a polar solvent, such as a simple ketone or ester, to the ether solution before evaporating the ether.

The hydrolysis reaction may be carried out by simply adding a polymerized silane to a hydrolyzing solution of an inorganic acid in water.

screamed;

tion would be required toeeffect the hydrolysis. It is, therefore, usuallyilprferable to carry out the hydrolysis in a mutual solvent (i. e., a soliarentssuchiaszxiioxane,aaeetone, cinethylzethyliket'one, methyll-ialcoholz or methyl alcohol, which .LiS iicapableicfi maintaining aanutualxzsolution of-lthe water, thel1-vaoid:.:and: the polymerized silane) s Anynamo-unt :of ..:'hy1drolyzing i solution'imay :be msed tirom 13,:"S1ightfi3l-3XCBSS over ilthe :Lminimum w'hichi is :theoreticallyzt required :to hydrolyze :the ipclymenizedssilane zii..ie.,:.one molecule of :water tater-eevery:two aalkoxysradicals) tiottheamaximum :amountcwhich permits aLOIIBphaSGJSYStEmTtO be emaintained. 'The;preferredrhydrolyzing solution 315 ran aqueous :mineral aacid :isolutionicontaining -aboutlO per cent of mineralsacidgizthe amount 20f thisshydroiyzinga'so-lutioniused issabout 50:.p81 icenteof'itheepoiymerfle'dasilane. 'i'Ihe eamountaof :zsolventfused rmayebeianyxamount#frorm the'minaims-mi required to v:maintain 1a one-phase system 411102111116 :zmaximum camount z'which is considered L' conomicallyspracticable. 'Iheiamountlofsolvent i lyzing solution,nalthoughhydrochlorioacid isrusu sally employed. The racidiunctionsrasa *catalyst for-the hydrolysis reaction, and even a 'traceiof waciid causes hydrolysis to ta'ke placesat aifrate that -is'i'at a' least appreciable (but not: necessarily .rapid enoughjfor practical use) :TIheamountof 3;,

azacicli usedmay range? from a trace,=:which rgives can? appreciable "effect; to ith'e" amount above :which 1: lie-"appreciable "increasein effect-can be obtained f (i: e.,: about 1 20 :per cent of the --polymerize'd 'si :tlane) "The spee'd .of -the" hydrolysisreaction is lidetermined essentially-by the amount of aci-d pr'esent 5 in j the hydrolysis solution; but the 131e-f f'ferrecl amount in a particular instanceis deter-- mined 2 also by -other C-fao'tors, such :as "that-eac- 'tiyity of the: polymerizedsilane-and the' extent of 1 polymerization (erg, high polymers seem -to' have a greateiutendency than low polymers-to gel "during-hydrolysis) :"Ihe hydrolysis reaction usually takes place at 1 ordinary -temperatures,- and "is slightly exothermic. -l-lydroly'sis -seems -to he 'complete within a few minutes, "abut anexten-ded "hydrolysis :reaction "-seems 1 to f-have: no harmful -effectson the product.

pre'ferable, foreconomicweasons, touse only a "comparatively short hydrolysis *reaction Ce. g about five r minutes) Therefore, "the time :of the hydrolysis reaction seems not to be'criticak'a-ndfit-is usually.

.314 :stioncofesi -fiwsiiilinka esrgorztheiformatiuneof .mew ;.vSi-eQ-+Si clinkages. The ;:he.teropolymers that have been hydrolyzed and partially or fully condensed appear to mndergo the same changes 115 as other siloxanes. iSince, in their use, the hyel0 A presence of air.

Example 1 A Grig-nard reaction betweerr'a methallyl-mag nesium halideand an alkyl orthosilicate =is use'd to produce *a methallyltrialkoxysilane,-- a "dimethallyldialkoxysilane, 'and a trlmethylallylalkoxy- -dilaneffonexamiole, the methylallylethoxysilanes, *aocor'dingitothe following procedure: A'charge oif *finely divi'de'd magnesium turnings (1008 grams) "is-put into a three-necked flask and the -fiask is then fitted -with' a dropping-funnel, a mercury-- sealed =stirrer and a reflux condenser equipped with a calcium chloride tube. .A"'- starter-=con- -sisting' of :a' bromo-substituted" hydrocarbon'in an :absclute *ether solution 15 ml. of ethy1 broniide riinitiate *-'a reaction) and the flask begins to- "get warm. -An alkyl ortho'silicate in an absolute ether solution 2080 -=gramsor ethyl orthosili'c'ate' in 45001 31. of ether) is added "to "the charge 330 throughthe dropping. funnel. Amethallylhalide "The resulting slurry, which contains -a large amount of grayish precipitate (mag-nesiumsalts') v 63822 grains of methallyl chloride) -is"then= added drop-wise (with stirring) through the dropping -f-unne1- at 'a rate sufficient-1y slow 'to'av0id 'vio1ent bdilrngo'ithe reaction mixture (over-a period of :l hours) "During the addition o'ft-he methaillyl "ha de'the fiask is pac'ked in ice and thetempera- -ture=of-=thecharge-remains at about 40 'C. .iAfter "the additiomof the methallyl halide iscompleted the material in thefla'sk is" refluxed for twohou-rs.

is cooled an'di' ii'ltered; *the' filter-"cake is 'wash'ed with an amount "of =-ether equal 1; to two "or -three =times the *volume' of the filtrate and the "ether F -is added to the 'filtrate. "The volatile materials Many practical"applications -crthe-hydrolyzed het eropolymersinvolve-their use-as solutionsi in solvents suchrassimple ketonespresters; or'the lower homologues of benzene. It is,*'therefore, *often' possible to-iuse-the solutionof *thehydro- "lyzedi polymer obtained after. evaporation ,of1the "extractings'olvent (e. g.,as a coatinggresiri).

In general; a partially condensed siloxane undergoes a change :in phys'ical properties When heated becominaealmore, viscous liquid .orsa solid. Although aifilly condensed siloxaneisextremely resistant further change due 'ztoil-ieah alone,

g., ether -and"bimetha1lyl-are distilledthrough a' g lass "helix packed-column at atmosphericprescsure by heating the' filtrate to' about' 125C.-an"d 'the'remain'cler "of the filtrate isseparateifby dls- *tillatiom-at 15" to 201mm. ,Hg (1. e.,;-'at" an "abso- 1 lute'pi'essure equal "toabout l5 'to'ZG'mm-oTmer- =cury') "to "obtain the :unreacted 'alkyl :;or;thosi1icate, the .methallylalkoxysilanes, intermediate cuts, :and :a "small amount :ofheavy .oilielikeiliqadd-bottoms. The'total s'ilane zproduct;recovered consists of'f234 grams of methallyltriethoxysilane "6B. -86 C. at 19" mmJI-Ijg; 11.4140;

120, r ld 0.9065) 6.0;4 L grams or fjdimethallyldielthoxysilane ,(B. 23?. :l02C. at ,18 mml'I-Igpn JLAQIO;

r wiazoseos) sure (B. P.), the index of: refraction at 20 C.

fture.

(12. and the specific gravity, 1. e., the density The proportion of each of the methallylalkoxysilanes in the product may be varied by varying the ratio of the reactants. A trimethallylalkoxysilane, in an appreciable proportion, does not result from the reaction of a methallyl magnesium halide and an alkyl orthosilicate in a molal ratio of less than about 3 :1. For example, when a molal ratio (of methallyl magnesium chloride to ethyl orthosilicate) of about 2:1 is used the product consists of about one part methallyltriethoxysilane to one part dimethallyldiethoxysilane, and when a molal ratio (of methallyl magnesium chloride to ethyl orthosilicate) within the range from about 1 to about 1:1 is used the product consists substantially of methallyltriethoxysilane.

The corresponding methoxy, propoxy, isopropoxy, n-butoxy, isobutoxy and secondary butoxy silanes are prepared by carrying out the procedures of the preceding paragraphs using methyl, propyl, isopropyl, n-butyl, isobutyl, or secondary butyl orthosilicate. Mixed esters of orthosilicic acid with methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, and secondary butyl alcohols may also be used, in which case mixed alkoxysilanes result.

, A Grignard reaction between an alkyl magnesium halide and a methallylalkoxysilane then is used to produce an alkylmethallyldialkoxysilane, a dialkylmethallylalkoxysilane or a dimethallylalkylalkoxysilane, for example, n-butylmethallyldiethoxysilane, and di(n-butyl)methallylethoxysilane, according -to the following procedure: A charge of finely divided magnesium turnings ('72 grams) is put into a three-necked flask and the flask is then fitted with a dropping funnel,

,a mercury-sealed stirrer and a reflux condenser equipped with a calcium chloride tube. A

starter consisting of a promo-substituted hydrocarbon-in an absolute ether solution (8 grams of n-butyl bromide in 25 ml. of ether) is added --to the charge (to initiate a reaction) and the flask begins to get warm. Dropwise addition of an alkyl halide (403 grams of n-butyl bromide) is then started. Absolute ether ('75 ml.) is added through the reflux condenser, and addition of the alkylhalide is continued at a rate sufilciently slow to avoid violent boiling of the reaction mix- After'the addition of the alkyl halide, which requires about six hours, a methallyltrialkoxysilane (218 grams of methallyltriethoxysilane) is added dropwise over a period of about one hour. The ether is then distilled from the mixture and the residue is heated strongly for eighthours. The solid cake of salts remaining in the flask is washed with benzene (about 1 /2 liters) and. filtered. The filter cake is well washed with benzene which is added to the filtrate. The volatile materials such as benzene are distilled from the filtrate through a glass helix packed column at atmospheric pressure by heating the filtrate to about 125 C., and the remainder of the filtrate is separated by distillation at about 10 to mm. Hg to obtain 76 grams of di(n-butyl)methallylethoxysilane (B. P. lid-119 C. at 13 mm. Hg; n 1.4410;

. aliylalkoxysilanes.

The proportions of the mono and dialkylsilanes in the product may be varied by varying the ratio of the reactants. Other alkyl halides may be used in the practice of the invention to produce the corresponding mono and dialkylmeth- The alkyl radical may be methyl, ethyl, n-propyl, isopropyl, isobutyl, secondary butyl, or a primary or secondary alkyl radical having from five to eight carbon atoms.

Maleic anhydride and a silane having at least one methallyl radical and at least one alkoxy radical then are polymerized according to the following procedures:

A methallyltrialkoxysilane (21.8 grams of methallyltriethoxysilane) and an equimolecular amount of maleic anhydride (9.8 grams) are mixed and benzoyl peroxide (1.6 grams) is, added. The mixture is heated on a steam bath. An almost explosive exothermic reaction occurs with the formation of a highly viscous material which continues to polymerize to a glass-like heteropolymer in from one to two minutes.

A methallyltrialkoxysilane (21.8 grams of -methallyltriethoxysilane) is heated by itself on a steam bath with benzoyl peroxide (0.22 gram) no noticeable polymerization takes place in thirty minutes. An equimolecular amount of maleic anhydride (9.8 grams) is dissolved in twice its volume of dioxane and mixed with the methallyltrialkoxysilane. This mixture is polymerized to a thick syrup at a controllable rate by heating on a steam bath for about ten minutes. A sample of the dioxane solution of the heteropolymer forms a rubbery white solid when poured into a hydrolyzing solution (e. g., a 5 per cent Water solution of hydrochloric acid). A film of the dioxane solution of the heteropolymer on a glass plate bakes to a hard, clear, colorless, somewhat brittle film in about thirty minutes at C.

A dimethallyldialkoxysilane (23 grams of dimethallyldiethoxysilane) is mixed in a 1:2 molal ratio with maleic anhydride (19.6 grams) in dioxane (50 ml.). Benzoyl peroxide (0.43 gram) is added to the mixture which is heated on a steam bath. Polymerization proceeds rapidly and exothermally in about fifteen minutes to yield a hard, colorless heteropolymer which is insoluble in the usual organic solvents such as the ketones, aliphatic alcohols and the lower homologues of benzene.

An n-butylmethallyldialkoxysilane (23.2 grams of n-butylmethallyldiethoxysilane) and an equimolecular amount of maleic anhydride (9.8 grams) are mixed; sufiicient methyl ethyl ketone (10 ml.) to form a one-phase solution is added, followed by benzoyl peroxide (0.33 gram). The mixture is warmed on a steam bath and very rapid exothermic polymerization takes place in less than one minute to yield a rubber-like heteropolymer which sets to a hard, colorless solid after standing for several days.

Example 2 A Grignard reaction between an ally] magnesium halide and a methallylalkoxysilane is used to produce an allylmethallylalkoxysilane, for example, allylmethallyldiethoxysilane, by a procedure that is the same as that described in the first paragraph of Example 1 except that the ingredients used are 48 grams of magnesium; 5 ml. of bromobenzene in 50 ml. of ether as the 17' starter ;1 4.50 grams of. methallyltriethoxysilane (111.75051111. (if, ether) 111.11318165191? ethyl orthosilicate; and: 175: grams of al-l-yl chloride instead of methallyl chloride. After the addition or the starter to; the. magnesium, the flask" is heated and. dropwise: addition of the allyl chloride is started. The methallyltriethoxrsilane and ether.

A maleic acid ester and a silane having at leastone .alkoxy radical and atleast oneme'thallyl radical are polymerized according to the fDflOVP- ing procedures;

A dimethallydialkox s'ilane (14A grams of di methallyldiethoxysilanel and an equimoiecu-lar amount of a, dialkyl maleate. (7.2 grams of di methyl malea'te) are mixed and benzoyl peroxide (0.22 gram) is added. 'This-rmixture is poly merized by heating in an electric oven for for-ty eighthours. a t.'57 C. The polymerization-"productis a. weak,;so.ft gel.

A.dimethallyl'dialkoxysiiane (14.4 grams/of di molalratiowith diallyl maleate (3952 grams) and 4 benzoyl peroxide (0.68 gram) is added. This mixture: is polymerized by heating in an electric oven for forty-eight hours at 75 C. The polymerization'product is a semi-hard solid which. becomes a very hard, tough, clear heteropolymer upon standing" for several days at room tern-e perature.

i A methall'yltrialkoxysilane (1019. grams of methallyltriethoxysilane) and an equimolecular amount of a dialkyl maleate. (10.0 grams. of dipropyl maleate) are mixed and benzoyl peroxido (0.21 grain)- is added. This mixtureis polymerized by heating in an electric; oven for fortyeight hours at) C; Thepolymerization prodnot is a low viscosity oil.

A metha-llyltrialkoxysilane (10.9 grams of methallyltriethoxysilane) and an equimol-ecular amount of a dialkylmaleate. (8.6 grams ot'diethyl maleate) are mixed and benzoyl. peroxide (6.20. gram). is added. This mixture isv polymerized by heating in an electric oven for forty-eight hours at C. Thev polymerization product is a low'viscosity'oil;

An:allylmethallyldialkoxysilane (19.7 grams of allylmethallyldiethoxysiiane) is mixed in. a 1:2 molal ratio with-a. dialkylmaleate (14.4: grams of dimethyl: maleate) and benzoyl peroxide (0.25 gram): is added. This mixture is. polymerized by heating in any electric oven for forty-eight hours at 7:0 6. The polymerization product is a low visoosityoil.

Example 3' A:Grignard: reaction between, an aryl or alkaryl halide and a methallylalkoxysilane is used to ether.

18 produce, an aryhnethallyilalkoxysilane, or an alka-rylmethallylalkoxysilane, for phenylmethallyldiethoxysilane and diph nylmethallylethoxysilane, by a procedure thatisthe same as that described in the firstparagraph of.

Example 1 except that the ingredients used are 72 grams of magnesium; 37 grams of bromobenzone and 25 ml. of ether, as the starter; 436 grams of methallyltriethoxysilane (in 7'75 ml. of ether); and 434 grams of bromobenzene. Dropwise addition of bromobenzene isstarted as. soon as the flask begins to get warm, and the metha'le lyltrieth-oxysilane and ether are, then, added through the reflux condenser. After all of, the

.- brom-o'benzene has been added, refluxing is conturned for three hours. The resulting reaction mixtureis cooled and filtered; the cake is washed with about one liter of dry benzene whichisadded to the filtrate; and the filtrate is distilled to yield. grams of diphenylmethallylethoxysilane, (B. .P..

180-185 C. at 17 mm. Hg; n 1.5259) and grams of phenylmethallyldiethoxysilane (B. P- 142-1446 C. at 20-21 mm. Hg; n 1.4840) A cycloalkylmethallylalkoxysilane, for ex mp i.

cyclohexylmethallyldiethoxysilane, is prepared by a. procedure that is the same as that described'i in, the first paragraph of Example 1 except th the ingredients are 24.3 grams of magnesium; 21

grams of methallyltriethoxysilane- (in 480 ml. of

7 other) in. place of ethyl. orthosilicate; and 163.

grams of cyclohexyl bromide instead of methallyl' chloride. and the Grignard reaction, is initiated by adding 7 grams of the cyclohexyl bromide in 20 ml. of The flask begins, to, get warm, and the. methallyltriethoxysilane (in the, ether solution) and 21 grams of the cyclohexyl bromide are added slowly tothe magnesium, over a period. of about fifteen minutes. After this addition ha been made, the remainder of the cyclohexyl bromide is added dropwise, over a period of about three" hours, and. the. resulting solution is refluxed for about one hour. The ether is distilled from the reaction. mixture until the temperature has risen to about 125 (3., and the reaction mixture is maintained at that temperature for about two to three hours, untilthe, liquid becomes thick from salts. \The ether is then reintroduced and the reactionmixture is refluxed for about four hours. The

. resulting reaction mixture is cooled and filtered;-

thecake is Washed with, benzene which is. added to the filtrate; and the filtrate is separated to yield 68. grams of cyclohexylmethallyidiethoxysilane (B. P. 133 C'.,.ati20 mm. Hg; 11 1.4560;

A cyclopentylmethallylalkoxysilane, for-- example, cyclopentylmethallyldiethcxysilane; is prepared" by carrying; out a procedure that is the same as that described in the preceding paragraph, except that the ingredients used are 24.3 grams of magnesium; 218 grams of" niethallyltriethoxy silane (in 295 m1. of ether); and 149- erams of cyclopentyl bromide. A starter consisting of 9 grams. of the cyc'lopentyl bromide in 15 ml; of ether, is added to the magnesium in the flask. When the reaction has started the methal lyltri ethoxysilane and the ether are added to the ma nesium; the remainder of the cyclopentyl bromide is added dropwise, over a period of about three hours; and the reaction mixture is held at about 70" C. for about one hour. The eth r is distilled from: the reaction mixture, which is then held. at about C. for about two hours, The

example,

The magnesium is placed in the flask,

Alkyl substituted cycloalkylmethallylalkoxysilanes, for example, 4 tertiary-amylcyclohexylmethallyldiethoxysilane, are prepared by carrying out a procedure that is the same as that described in the preceding paragraph except that the ingredients used are 33.6 grams of magnesium; 305.2 grams of methallyltriethoxysilane (in 80 ml. of ether) and 326.2 grams of 4-tertiaryamylcyclohexyl bromide. The starter consists of 6.2 grams of the 4-tertiary-amylcyclohexyl bromide in 20 ml. of ether. Dropwise addition of the 4-tertiary-amylcyclohexyl bromide requires about three and one-half hours. After the reaction mixture has been held at about 70 C. for one hour the ether is distilled, and the reaction mixture is held at about 135 C. for about four hours. The reaction mixture is cooled and filtered; the filter cake is washed with ether which is added to the filtrate; and the filtrate is separated to yield 130 grams of 4-tertiary-amylcyclohexylmethallyldiethoxysilane (B. P. 157-162 C. at mm. Hg; n 1.4639;

Other alkyl-substituted cycloaliphatic halides as hereinbefore described may be used in place of 4-tertiary-amylcyc1ohexyl bromide.

A benzylmethallyldialkoxysilane and a dibenzylmethallylalkoxysilane, for example, benzylmethallyldiethoxysilane and dibenzylmethallylethoxysilane, are. prepared by a procedure that is the same as that described in the first paragraph of Example 1 except that the ingredients are 48 grams of magnesium, 253 grams of benzyl chloride, and 218 grams of'methallyltriethoxysilane (in 975 ml. of ether). A starter consisting of 5 ml. of ethyl bromide in 25 ml. of ether is added to the magnesium in the flask. As soon as the reaction has started, dropwise addition of the benzyl chloride is begun, and the ether solution of methallyltriethoxysilane is added through the reflux condenser. Dropwise addition of the benzyl chloride is continued at a rate sufiicient to maintain moderate refluxing of the ether. After the addition of benzyl chloride is completed, the reaction mixture is refluxed for about 24 hours, and the ether is then removed from the reaction mixture by distillation. Toluene (500 ml.) is added, and the resulting mixture is refluxed for about 6 hours. The reaction mixture is cooled and filtered; the cake is washed with toluene (500 ml); the filtrate and washings are placed in a Claisen flask; and the toluene is distilled. Further precipitation accompanies distillation of the toluene. The reaction mixture is separated from the salts in the Claisen flask and is fractionated under reduced pressure to yield 50 grams of benzylmethallyldiethoxysilane (B. P. 106 C. at 4 mm. Hg; n 1.4973;

and. 15 grams of a yellow product (B. P. 140-150" C. at 3 mm. Hg) which consists substantially of dibenzylmethallylethoxysilane.

An ester of fumaric acid and a silane having at least one alkoxy radical and at least one methallyl radical are polymerized according to the following procedures:

A methallylalkoxysilane (2.2 grams of methallyltriethoxysilane) is mixed in a 1:1 molal ratio with a dialkyl fumarate (1.7 grams of diethyl fumarate), and benzoyl peroxide (0.04 gram) is added. This mixture is polymerized by heating in an electric oven for twenty-four hours at 75 C. The polymerization product is a, thick, colorless syrup.

The procedure of the preceding paragraph is repeated using, as the methallylalkoxysilane: 1. phenylmethallyldiethoxysilane (2.5 grams); 2. n-butylmethallyldiethoxysilane (2.3 grams); or 3. diphenylmethallylethoxysilane (2.8 grams). In each case the polymerization product is a colorless syrup.

A dimethallyldialkoxysilane (22.8 grams of dimethallyldiethoxysilane) is mixed in a 1:2 molal ratio with a dialkyl fumarate (34.4 grams of diethyl fumarate), and benzoyl peroxide (0.57 gram) is added. This mixture i polymerized by heating in an electric oven for twenty-four hours at 75 C. The polymerization product is a rubbery, insoluble gel.

A methallyltrialkoxysilane (21.8 grams of methallyltriethoxysilane) is mixed in a 1:1 molal ratio with diallyl fumarate (19.6 grams), and benzoyl peroxide (0.41 gram) is added. This mixture is polymerized by heating in an electric oven for six hours at 75 C. The polymerization product is a soft gel.

A dimethallyldialkoxysilane (22.8 grams of dimethallyldiethoxysilane) is mixed in a 1:2 molal ratio with diallyl fumarate (39.2 grams), and benzoyl peroxide (0.62 gram) is added. This mixture is polymerized by heating in an electric oven for one hour at 75 C. The polymerization product is a hard, clear, colorless resin.

A dimethallyldialkoxysilane (11.4 grams of dimethallyldiethoxysilane) is mixed in a 1:2 molal ratio with di-(Z-ethylhexyl) fumarate (34.0 grams), and benzoyl peroxide (0.45 gram) is added. This mixture is polymerized by heating in an electric oven for forty-eight hours at C. The polymerization product is a high viscosity, colorless syrup.

An allylmethallyldialkoxysilane (10.7 grams of allylmethallyldiethoxysilane) is mixed in a 1:2 molal ratio with a dialkyl fumarate (17.2 grams of diethyl fumarate), and benzoyl peroxide (0.28 gram) is added. This mixture is polymerized by heating in an electric oven for forty-eight hours at 70 C. The polymerization product is part high viscosity, colorless syrup and part gel.

A benzylmethallyldialkoxysilane (13.2 grams of benzylmethallyldiethoxysilane) and an equimolecular amount of a dialkyl fumarate (8.6 grams of diethyl fumarate) are mixed and benzoyl peroxide (0.22 gram) is added. This mixture is polymerized by heating in an electric oven for forty-eight hours at 70 C. The polymerization product is a low viscosity oil.

A 4-tertiary-amylcyclohexylmethallyldialkoxysilane (32.6 grams of 4-tertiary-amylcyclohexylmethallyldiethoxysilane) and an equimolecular amount of a dialkyl fumarate (17.2 grams of diethyl fumarate) are mixed and benzoyl peroxide (0.50 gram) is added. This mixture is polymerized by heating in an electric oven for 60 hours at 7 0 C. The polymerization product is a viscous liquid. The viscous liquid is placed in a Claisen flask and distilled at 4 mm. Hg, the liqroom temperature.

uid being heated to 230 C. The distillate comprises about 6 grams of themonomers and about 6 grams of a material (having a'boiling point of 129-130 C. at 4 mm. Hg) which solidifies at Thus, the total distillate is about 12 grams, and the undistillable residue is about 31 grams.

A cyclopentylmethallyldialkoxysilane (24.2 grams of cyclopentylmethallyldiethoxysilane) and an equimolecular amount of a dialkyl fumarate (17.2 grams of diethyl iumarate) are mixed and benzoyl peroxide (0.41 gram) is added. This mixture is polymerized by heating in an electric oven for 60hours at 70 C. The polymerized product is a viscous liquid.

A cyclohexylmethallyldialkoxysilane (25.6 grams of cyclohexyl-methallyldiethoxysilane) and an equimolecular amount of a dialkyl fumarate (17.2 grams of diethyl fumarate) are mixed and benzoyl peroxide (0. 13 gram) is added. This mixture is polymerized by heating in an electric oven for 60 hours at 70 C. The polymerization product is a viscous liquid. Benzoyl peroxide (0.86 gram) is added to this polymerization product, and the liquid is then placed in the electric oven ioran additional 65 hours; no apparent increase in viscosity occurs.

Example 4 Theiusible polymerizedsilanes of the invention may be hydrolyzed and condensed to siloxanes. This example demonstrates one of the difiiculties (the tendency of the hydrolyzed heteropolymer to gel during its recovery from the hydrolysis solution) encountered in hydrolyzing the heteropolymers, and illustrates several ways of overcomingthis difliculty.

A heteropolymer of methallyltriethoxysilane (185 grams) and diethyl fumarate (150 grams) is prepared, using benzoyl peroxide (3.35 grams), by heating in an electric oven for seventy two hours at 75 C. The polymerization product, a colorless, viscous syrup, is hydrolyzed by dropping into a stirred mixture of a 7 per cent aqueous hydrochloric acid solution (200 ml.) and ethyl alcohol (200 ml.) at room temperature. After one hour of stirring, the resulting one-phase hydrolysis mixture is poured into a separatory fun-.

nel containing about an equal volume of water. The mixture in the separatory funnel is then shaken and extracted twice with ether (in 200 m1. portions). The ether extracts are combined and dried over anhydrous sodium sulfate, which is then separated by filtration, and the ether is removed by evaporation on a steam bath. Near the completion of the ether evaporation th viscous liquid gels; the. gel, is insoluble in toluene and xylene.

The following demonstrations illustrate ways of preparing hydrolyzed heteropolymers that avoid the gelling encountered in the procedure described in the preceding'paragraph.

A mixture, of methallyltriethoxysilane (116 grams) and, diethyl fumarate (94 grams) is prepared, and benzoyl peroxide (2.10 grams) is added. This mixture is divided into three equal portiongby volume which are placed in an electric oven atv 75 C. to polymerize. Sample 1 is removed after eighteen hours; sample 2 is removed after twenty-four hours; and sample 3 is removed after forty-six hours. A test of the viscosity of each heteropolymer is made by measuring the time required for the heteropolymer to flow from a 25ml. pipette-at a temperature of 25 22 C. The efflux times are 143.0,2115andi259;7=seconds for samples 1, 2 and 3, respectively.

Sample 1 is hydrolyzed by pouring it .into :a stirred mixture of a '7 per centaqueous hydrochloric acid solution (35 ml.) and ethyl alcohol "('35 ml.). The hydrolysis mixture is stirred vigorous- 1y forfive minutes; ether (about 70 ml.) is added and the mixture is transferred to a separatory funnel. About an equal volume of -waterxissadded to the s-eparatory funnel, the funnel is shaken, and the etherlayeristhen'separated. The water solution is re-extracted with ether (about '70 ml.) and'the combined ether extracts are'dr'ied'over sodium sulfate. Thesodium sulfate is removed by filtration, and evaporation of the ether is started on a steam bath. When'mostof the ether has evaporated, a toluene (50 ml.) is added and the solution is further heated-'ona steam bath to evaporate the remaining ether. This procedure avoids gelling. A film of the resulting toluenesolution of the heteropolymer dries tack-free in less than one hour at"1i0 'C. The film is clear and hard but rather friable; baking for twelvehours at 140 C. causes crazing of the film. The toluene solution gels after standing aboutseven'twtwohours.

Sample 2 is hydrolyzed by the procedure used to hydrolyze Sample 1. However, the toluene-ether solution of the hydrolyzed heteropolymergels dur ing evaporation of the-ether.

Sample 3 is hydrolyzed by'pourin'g it into a stirred mixture of a '7 percent aqueous'hydro'chlm ric acid solution ('35 ml.) andethyl alcohol (35 ml.) The hydrolysis-mixture issti-rred vigorously for five minutes; ether "(about'140-ml.) is added and the mixture is transferred to a separatory funnel. About an equal volume of water is added to the separatory funnel; the ether layer is separated, and washed twice with about 25 ml. of a 5 per cent aqueous ferrous sulfate solution. The ether extract is dried over sodium sulfate, and the sodium sulfate is removed by filtration. Hydroquinone (0.7 gram) is added to the'ether solution, followed by toluene (50 ml.). The ether is evaporated gently on a steam bath. This procedure avoids gelling. A film of the toluene solution of the hydrolyzedheteropolymerremains tacky after extended heatingat 140 C.

A mixture. of methallyltriethoxysilane (87:2 grams), diethyl fumarate (68.2 grams) and benzoyl peroxide (1.6 grams) is polymerized by heating in an electric ovenfor twenty-four hours at. C. The viscosity is. measured as described above; the-.efilux time at 25 C. is 1'7:9.0"second's. The. heteropolymer is hydrolyzed by pouring :it into a stirred mixture of a 7 per cent aqueous hydrochloric acid solution. (about ml.) and ethyl alcohol (about 80 ml'.).. The hydrolysis mixture is stirred vigorously for'five minutes; ether. (about 300 ml.) is added and the mixture is transferred to a separatory' funnel. About an equal volume of water .isadded to the separatory funnel; the ether layer is separated, and washed twice with about 25 ml. of a 5 per cent aqueous ferrous sulfate solution. The ether extract i's-driedover sodium sulfate, and the sodium sulfate is removed by filtration. Toluene (150 ml.) is added, and the ether is evaporated gently on a steam bath. This procedure avoids gelling. A film of the toluene solution of the hydrolyzed heteropolymer cures tack-free in about one hour at C., but" the film is soluble in acetone until it has cured about three hours at 140 C. The film is clear, hard and free oi cracks.

A sample of the toluene solution of the *hydrolyzed heteropolymer (about three parts) is diluted with acetone (about one part) to reduce the viscosity. The acetone-diluted solution is used to prepare a glass fiber laminate by dipping eight sheets of glass fiber cloth in the solution, suspending the sheets in air for about twenty minutes to allow drainage and solvent evaporation, and pressing the impregnated sheets of fiber glass between two glass plates (smeared with a commercial mold release fiuid). The glass plates are subjected to pressure by clamps, and the laminate is placed in an electric oven for about fifteen hours at 140 C. The resulting laminate is hard and has good flexibility.

The remaining toluene solution forms a soft gelafter standing'for several days. This gel, however, is soluble in acetone, and the acetone solutiorr remains stable for an extended period' ,oftime. A film of this acetone-toluene solution of the hydrolyzed heteropolymer cures completely in about three hours at 140 C. The resulting film is superior to one from the freshly prepared toluene solution of the hydrolyzed heteropolymer; no crazing or discoloration is observed after the film is heated for seventy-two hours at 145 C. The film appears to be unaffected by immersion for one hour in boiling water, and appears to be completely insoluble in acetone and hydrocarbon solvents.

A mixture of methallyltriethoxysilane (87.2

grams), diethyl fumarate (68.2 grams) and benzoyl peroxide (1.6 grams) is polymerized by heating in an electric oven for twenty-four hours at 75 C. The heteropolymer is hydrolyzed by pouring it into a stirred mixture of a 7 per cent aqueous hydrochloric acid solution (about 80 ml.) and ethyl alcohol (about 80 ml). The hydrolysis mixture is stirred vigorously for five minutes; ether (about 300 ml.) is added and the mixture is transferred to a separatory funnel containing about an equal volume of water. The funnel is shaken; the ether layer is separated, and washed twice with about 25 ml. of a per cent aqueous ferrous sulfate solution. The ether extract is dried over sodium sulfate, and the sodium sulfate is removed by filtration. Methyl ethyl ketone (about 300 ml.) is added, and the ether is evaporated gently on a steam bath. This procedure avoids gelling. A film of the methyl ethyl ketone solution of the hydrolyzed heteropolymer cures in about thirty minutes at 145 C. to a hard film, insoluble in acetone. The film apparently is unaffected by boiling water, or by three weeks soaking in a 9 per cent aqueous hydrochloric acid solution. A 3 per cent aqueous KOI-I solution causes the film to crack and to peel from the plate in twelve hours. No crazing was observed in the film after seventy-two hours at 145 0.; however, cracking of the film was observed after seventytwo hours at 180 C.

Example 5 A mixture of phenylmethallyldiethoxysilane grams), an equimolecular amount of diethyl fumarate (17.2 grams), and benzoyl peroxide (0.42 gram) is polymerized by heating in an electric oven for twenty-four hours at 75 C. The polymerization product, a viscous syrup, is hydrolyzed by pouring it into a stirred mixture of a 7 per cent aqueous hydrochloric acid solution (about ml.) and ethyl alcohol (about 30 ml.) at room temperature. The resulting onephase hydrolysis mixture is stirred for about five minutes and is then poured into a separatory 24 funnel containing about an equal volume of water. The mixture in the separatory funnel is then shaken and extracted with ether (about ml.). The ether solution is dried over anhydrous sodium sulfate, which is then separated by filtration, and the ether is removed by evaporation on a steam bath. When most of the ether has evaporated, toluene (25 ml.) is added, and the solution is further heated on a steam bath to evaporate the remaining ether. A film of the toluene solution of the hydrolyzed heteropolymer, when baked for seventy-two hours at 145 0., remains slightly thermoplastic at that temperature, but, upon cooling in the air, a hard brittle film results.

Example 6 A mixture of. n-butylmethallyldiethoxysilane (5.8 grams), diethyl fumarate (4.3 grams) and benzoyl peroxide (0.1 gram) is polymerized by heating in an electric oven for twenty-four hours at 75 C. The polymerization product, a viscous syrup, is hydrolyzed by pouring it into a stirred mixture of a 7 per cent aqueous hydrochloric acid solution (about 10 ml.) and ethyl alcohol (about 10 ml.) at room temperature. The resulting one-phase hydrolysis mixture is stirred for about five minutes and is then poured into a separatory funnel containing about an equal volume of water. The mixture in the separatory funnel is then shaken and extracted with ether (about 40 ml). The ether extract is dried over anhydrous sodium sulfate, which is separated by filtration. The evaporation of the ether is started on a steam bath; when most of the ether has evaporated, toluene (about 10 ml.) is added and the solution is further heated on a steam bath to evaporate the remaining ether. A film of the toluene solution of the hydrolyzed heteropolymer dries in three hours at C. to a hard, clear, crack-free film.

Having described the invention, I claim:

1. A polymerizable composition comprising (1) a substance of the class consisting of maleic anhydride and esters of 1,2-ethylenedicarboxylic acids in which each of the alcohol radicals is of the class consisting of allyl, methallyl, l-chloro- Z-propyl, 2-chloro-ethyl, benzyl, tetrahydrofurfuryl, cyclohexyl, phenyl, cresyl, and alkyl radicals having from one to eight carbon atoms and having at least one hydrogen atom attached to the same carbon atom as the oxygen atom; and (2) a substance of the class consisting of those having the general formulas in which R is an alkoxy radical having from one to four carbon atoms and having at least one hydrogen atom attached to the same carbon atom as the oxygen atom; each of the radicals A and A is of the class consisting of allyl, methallyl, benzyl, alkyl radicals having from one to eight carbon atoms and having at least one hydrogen atom attached to the same carbon atom as the free valence, monovalent aromatic hydrocarbon radicals having the free valence attached to a nucleus, having not more than two benzene nuclei that contain not more than ten carbon atoms, having from six to twenty-five carbon atoms, and having not more than three side chains consisting of alkyl radicals of not more than five carbon atoms, and radicals of the same class as R; b is a monovalent cycloaliphatic hydrocarbon radical having a single nucleus con-v ,,taining from .,five to 'six carbon atoms .one of the rest of :whichare each connected to .at least one hydrogen atom, having from five to sixteen carbon atoms, vand having not more than two side chains consisting of alkyl radicals of ,notmore than five carbon atoms; and 33 is of the classconsisting of radicals of the same class as "b and R, the molar ratio of the first mentioned substance to the last mentioned substance being at least one and being not more than the numbero'f methall-yl'radicals per molecule of the last mentioned substance.

H .2. .A,polymerizable composition as claimed in a claim 1 ,in which the first-mentioned substance is an ester of a 1,;2- -ethylenedicarboxylic acid wherein ,each alcohol radical is an alkyl radical ihavin'gfrom one to eight carbon atoms and hav- "ingat least one hydrogen atom attachedto the r same carbon atom as the ,oxygenatom.

.The produot of the addition polymerizaitionlof acomposition claimedin claim 1.

The product of the addition polymerization j of a compositionias claimed in claim ,1 in which the first-mentioned substance is an ester of a "l,'2-ethylenedicarboxylic acid wherein each alcohol radical is an alkyl radical having from one to eight carbon atomsand having at least one'hydrogenatom attached to the same carbon atom as the oxygen atom.

5. ,A ,polymerizable composition as claimed in claim 1 in which the second-mentioned substance is one having the general formula ,in which n is? an integer from .1 to ,2 and the sum of m and n is from 1 to 2; each of the radicals MR ,and R is an alkoxy radical having from one i3. :Apolymerizable composition as claimed in wclaim 1 -1 :in which the second-mentioned sub- ;stance one having the. generalformula in which each of the radicals R and R. is an alkoxy radical having from one to four carbon atoms and having at least one hydrogen atom attached to the same carbon atom as the oxygen atom; and b is a monovalent cycloaliphatichy- 'drocarbon'radicalhaving a single nucleus containing from five to six carbon atoms one of which is connected 'to'the freevalence and to a first, is connected to two hydrogen atoms, and

V the rest of which are each connected to at least one hydrogen atom, having iromrfive to sixteen carbon atomsandhaving .not more than two side chains consisting .of alkyl radicals of 'not more thanxfive carbon atoms.

hydrogen atom, another =01" which, adjacent the 26 "7. A ,polymerizable composition as claimed in claim 1 in which the second-mentioned substance is one having the general formula in which each of the radicals R and R is :an alkoxy radical having from one to four carbon vatoms andhaving at least one hydrogen atom attached to the same-carbon'atom as the oxygen atom; and .t is .a-monovalent aromatic hydrocarbon radical having the free valence attached to a nucleus, having not more than two benzene nuclei that contain not more than ten carbon atoms, having from 'six' to twenty-five carbon atoms, and having not more than three side chains consisting of alkyl radicals of notmore than'fivecarbonatoms. 7

8. The product of the addition polymerization of a composition as claimed in claim 1 in-which the second-mentioned substance is one having in whichn is an integer fromll to 2 and the sum of m and n .is from 1 to 2; each of theiradicals R and R is an alkoxy radical having from one to four carbon atoms and having at least one hydrogenatom attached to the same carbonvatom as the oxygen atom; and a .is an alkylradical having from oneto eight carbon atoms andLhaving at least one hydrogen atom attached to the same carbon atom as the .free valence.

9. The product of the addition polymerization of a composition as claimed in claim 1 in which the second-mentioned substance is one having the general formula in which each of the radicals Band B. .is .an alkoxy radical having from one to four carbon atoms and having .at least one hydrogen. atom .attachedto the same carbon-atom as the oxygen atom; and b is a monovalent cycloaliphatio hydrocarbon radical having a single nucleus containing from five to sixrcarbon atoms one of which is connected to the tree valence and to a hydrogen atom, another of which, adjacent the first, is connected to two hydrogen atoms, and the rest of which are each connected to atleast one hydrogen atom, having from live to sixteen carbon atoms, and having not more than two side chains consisting of alkyl radicals of not more than five carbon-atoms.

'10. The product of the'addition polymerization of a composition as claimed in claim 1 in which the second-mentioned substance is one having "the general formula in which eac'hiof theradicalsR'and'R' is an alkoxy radical having from one to four carbon atoms'an'd having at least one hydrogen atom attached ttothesamecarbon atom as the oxygen atom; and it is a monovalent aromatic 'hydro carbon radical having the free valenceattached to a'nucleusj'havingnot more than two fbenzene nuclei that contain not more than ten carbon atoms, having from six to twenty-five carbon atoms, and having not more than three side chains consisting of alkyl radicals of not more than five carbon atoms.

11. A polymerizable composition comprising a substance which is an ester of a 1,2-ethylenedicarboxylic acid wherein each alcohol radical is an alkyl radical having from one to eight carbon atoms and having at least one hydrogen atom attached to the same carbon atom as the oxygen atom; and a substance having the general formula in which n is an integer from 1 to 2 and the sum of m and 12, is from 1 to 2; each of the radicals R and R is an alkoxy radical having from one to four carbon atoms and having at least one hydrogen atom attached to the same carbon atom as the oxygen atom; and a is an alkyl radical having from one to eight carbon atoms and having at least one hydrogen atom attached to the same carbon atom as the free valence, the molar ratio of the first mentioned substance to the last mentioned substance being at least one and being not more than the number of methallyl radicals per molecule of the last mentioned substance.

12. A polymerizable composition as claimed in claim 11 in which n is 1.

13. The product of the addition polymerization of a composition claimed in claim 11.

14. The product of the addition polymerization of a composition as claimed in claim 11 in which n is 1.

15.'The product of the hydrolysis and condensation of the addition polymerization prodnot claimed in claim 14.

16. A polymerizable composition comprising a substance which is an ester of a 1,2-ethylenedicarboxylic acid wherein each alcohol radical is an alkyl radical having from one to eight carbon atoms and having at least one hydrogen atom attached to the same carbon atom as the oxygen atom; and a substance having the general formula in which each of the radicals R and R is an alkoxy radical having from one to four carbon atoms and having at least one hydrogen atom attached to the same carbon atom as the oxygen atom; and b is a monovalent cycloaliphatic hydrocarbon radical having a single nucleus containing from five to six carbon atoms one of Y which is connected to the free valence and to a hydrogen atom, another of which, adjacent the first, is connected to two hydrogen atoms, and the rest of which are each connected to at least one hydrogen atom, having from five to sixteen carbon atoms, and having not more than two side chains consisting of alkyl radicals of not more than five carbon atoms, the molar ratio of the first mentioned substance to the last mentioned substance being at least one and being not more than the number of methallyl radicals per molecule of the last mentioned substance.

' 1'7. The product of the addition polymerization of a composition claimed in claim 16.

18. The product of the hydrolysis and condensation of a product of the addition polymerization of a composition claimed in claim 16.

19. A polymerizable composition comprising a substance which is an ester of a 1,2-ethylenedicarboxylic acid wherein each alcohol radical is an alkyl radical having from one to eight carbon atoms and having at least one hydrogen atom attached to the same carbon atom as the oxygen atom; and a substance having the general formula in which each of the radicals R. and R is an alkoxy radical having from one to four carbon atoms and having at least one hydrogen atom attached to the same carbon atom as the oxygen atom; and t is a monovalent aromatic hydrocarbon radical having the free valence attached to a nucleus, having not more than two benzene nuclei that contain not more than ten carbon atoms, having from six to twenty-five carbon atoms, and having not more than three side chains consisting of alkyl radicals of not more than five carbon atoms, the molar ratio of the first mentioned substance to the last mentioned substance being at least one and being not more than the number of methallyl radicals per molecule of the last mentioned substance.

20. The product of the addition polymerization of a composition claimed in claim 19.

21. The product of the hydrolysis and condensation of a product of the addition polymerization of a composition claimed in claim 19.

22. A polymerizable composition comprising a substance of the class consisting of maleic anhydride, and esters of 1,2-ethylenedicarboxylic acids in which each of the alcohol radicals is of the class consisting of allyl, methallyl, 1- chloro-Z-propyl, 2-chloroethyl, benzyl, tetrahydrofurfuryl, cyclohexyl, phenyl, cresyl, and alkyl radicals having from one to eight carbon atoms and having at least one hydrogen atom attached to the same carbon atom as the oxygen atom; and a substance having the general formula in which n is an integer from 1 to 3, and R is an alkoxy radical having from one to four carbon atoms and having at least one hydrogen atom attached to the same carbon atom as the oxygen atom, the molar ratio of the first mentioned substance to the last mentioned substance being at least one and being not more than the number of methallyl radicals per molecule of the last mentioned substance.

23.'A polymerizable composition as claimed in claim 22 in which the first-mentioned substance is an ester of a 1,2-ethylenedicarboxylic acid wherein each alcohol radical is an alkyl radical having from one to eight carbon atoms and having at least one hydrogen atom attached to the same carbon atom as the oxygen atom.

24. A polymerizable composition as claimed in claim 22 in which the last-mentioned substance has the general formula ga oH2=c -cn, .si -0-o11z-orn)(4a.) in which n is an integer from 1 to 3.

25. The product of the addition polymerization of a composition claimed in claim 22.

26. The product of the addition polymerization of a composition as claimed in claim 22 in which the first-mentioned substance is an ester of a 1,2-ethylenedioarboxylic acid wherein each alcohol radical is an alkyl radical having from one to eight carbon atoms and having at least one hydrogen atom attached to the same carbon atom as the oxygen atom.

27. The product of the addition polymerization of a composition as claimed in claim 22 in which the last-mentioned substance has the general formula CHa (CHz=JCHz-)..Sl(-0-CHz-CHa)u-. in which n is a number from 1 to 3. V

28. A copolymer of (1) an ester of a 1,2-ethylenedicarboxylic acid wherein each alcohol radical is an alkyl radical havin'gi from one to eight carbon atoms and having at least one hydrogen atom attached to the same carbon atom as the oxygen atom; and (2) a substance having the general formula CH3 om=c-cur ),.si -o-cm-o a)(4-,) in which n is an integer from'i to 3. the molar ratio of the first mentioned substance to the last mentioned substance being at least one and being not more than the number of methallyl radicals per molecule of the last mentioned substance.

RAYMOND H. BUNNELL.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,945,307 Dykstra Jan. 30, 1934 2,377,689 Hyde June 5, 1945 2,388,161 Kropa Oct. 30, 1945 2,413,582 Rust et a1 Dec. 31, 1946 2,420,912 Hurd May 20, 1947 2,443,740 Kropa June 22, 1948 2,450,594 Hyde Oct. 5, 1948 2,465,731 Kropa Mar. 29, 1949 2,502,286 Sowa Mar. 28, 1950 2,532,583 Tyran Dec. 5, 1950 FOREIGN PATENTS Number Country Date 624,361 Great Britain June 7, 1949 

1. A POLYMERIZABLE COMPOSITION COMPRISING (1) A SUBSTANCE OF THE CLASS CONSISTING OF MALEIC ANHYDRIDE AND ESTERS OF 1,2-ETHYLENEDICARBOXYLIC ACIDS IN WHICH EACH OF THE ALCOHOL RADICALS IS OF THE CLASS CONSISTING OF ALLYL, METHALLYL, 1-CHLORO2-PROPYL, 2-CHLORO-ETHYL, BENZYL, TETRAHYDROFURFURYL, CYCLOHEXYL, PHENYL, CRESYL, AND ALKYL RADICALS HAVING FROM ONE TO EIGHT CARBON ATOMS AND HAVING AT LEAST ONE HYDROGEN ATOM ATTACHED TO THE SAME CARBON ATOM AS THE OXYGEN ATOM; AND (2) A SUBSTANCE OF THE CLASS CONSISTING OF THOSE HAVING THE GENERAL FORMULAS 